Method of coloring porous material

ABSTRACT

A method of coloring porous material, especially human hair, is described, which method comprises applying to the material being colored, in any desired order successively, or simultaneously, a) a capped diazonium compound and b) a water-soluble coupling component under conditions such that, initially, coupling does not take place, and then causing the capped diazonium compound present on the material to react with the coupling component.

The present invention relates to a method of colouring porous material,for example metal, wood or keratin-containing fibres, especially humanhair, using developing dyes, that is to say dyes which are formed insidethe pores of the substrate.

Colouring with the aid of developing dyes has been known for a long timeand has also been generally used for dyeing cotton. The dyes and thecolouring methods used therefore do not, however, provide satisfactoryresults for colouring hair.

For colouring hair, therefore, oxidation dyes are used in most cases;however, they too are not capable of satisfying all requirements. Thefastness to washing properties are often inadequate and, in addition,the colouring conditions required often cause a greater or lesser amountof damage to the hair. There has therefore been a need for a colouringmethod which does not have the mentioned disadvantages or which has themto an insignificant degree.

The present invention relates to a method of colouring porous material,which comprises applying to the material being coloured, in any desiredorder successively, or simultaneously,

-   -   a) a capped diazonium compound and    -   b) a water-soluble coupling component        under conditions such that, initially, coupling does not take        place, and then causing the capped diazonium compound present on        the material to react with the coupling component.

The colorations obtained are distinguished by outstanding fastness towashing properties, which are significantly better than in the case ofcolorations with oxidation dyes, and there is virtually no damage to thehair. Moreover, there is no staining of the scalp, because the dyecomponents do not penetrate into the skin and non-fixed dye can bewashed off readily.

Suitable capped diazonium compounds include, for example, antidiazoatesof formula

diazosulfonates of formula

diazines of formula

and also cyclic triazenes of formula

In formulae (1) to (5):

-   A is the organic residue of an unsubstituted or substituted aromatic    or heterocyclic amine,-   B is the radical of an unsubstituted or substituted, water-soluble    aliphatic or aromatic amine and-   R is an unsubstituted or substituted alkyl group,-   wherein at least one of the groups must contain a radical imparting    water solubility.

Suitable radicals imparting water solubility include, for example, SO₃H,COOH, OH or a quaternised ammonium radical of formula

wherein R₁, R₂ and R₃ are each independently of the others unsubstitutedor substituted alkyl and An is an anion.

According to the invention, alkyl groups R, R₁, R₂ and R₃ are to beunderstood as being generally open-chain or branched alkyl radicals, forexample methyl, ethyl, n- or iso-propyl and n-, sec- or tert-butyl.

Such alkyl radicals may be mono- or poly-substituted, for example byhydroxy, carboxy, halogen, cyano or by C₁–C₄alkoxy.

Preferably, the alkyl groups are unsubstituted and each has from 1 to 4,especially 1 or 2, carbon atoms.

Suitable anions An are both inorganic and organic anions, for examplehalide, such as chloride, bromide or iodide, sulfate, hydrogen sulfate,methyl sulfate, formate, acetate and lactate.

The anion is generally determined by the preparation process.Preferably, the chlorides, hydrogen sulfates, sulfates, methosulfates oracetates are present.

A is the radical of an unsubstituted or substituted aromatic orheterocyclic amine. For example, unsubstituted or substituted radicalsof aminobenzene, 1- or 2-aminonaphthalene, 2-aminothiophene,2-amino-1,3-thiazole, 5-amino-1,2-thiazole, 2-amino-1,3-benzothiazole,1-amino-2,3-benzothiazole, 2-aminoimidazole, 2-amino-1,3,4-thiadiazole,2-amino-1,3,5-thiadiazole, 2-amino-1,3,4-triazole, 3-, 7- or8-aminopyrazole, 2-aminobenzimidazole, 2-aminobenzopyrazole, 2- or4-aminopyridine, 2-, 3-, 4-, 7- or 8-aminoquinoline, 2-amino-pyrimidineand 3-aminoisoxazole, 5-aminoquinoline, 4-aminodiphenylamine,2-amino-diphenyl ether and 4-aminoazobenzene are suitable.

Such radicals may be mono- or poly-substituted, for example byC₁–C₄alkyl, C₁–C₄alkoxy, C₁–C₄alkylthio, halogen, e.g. fluorine, bromineor chlorine, nitro, trifluoromethyl, CN, SCN, C₁–C₄alkylsulfonyl,phenylsulfonyl, benzylsulfonyl, di-C₁–C₄alkylaminosulfonyl,C₁–C₄alkyl-carbonylamino, C₁–C₄alkoxysulfonyl or bydi-(hydroxy-C₁–C₄alkyl)-aminosulfonyl.

Examples of suitable radicals A are as follows:

B is the radical of an unsubstituted or substituted, water-solublealiphatic or aromatic amine, especially suitable aliphatic amines beingthose carrying a carboxylic acid or sulfonic acid group, for examplemethylaminoacetic acid (sarcosine), methylaminobutyric acid,methylaminopropionic acid, ethylaminoacetic acid, ethylaminobutyricacid, 1-methylamino-ethane-2-sulfonic acid,1-ethylamino-ethane-2-sulfonic acid and 1-methylamino-propane-3-sulfonicacid are suitable.

Aromatic amines that are suitable for B are especially aniline andaminonaphthalene compounds, more especially those carrying a carboxylicacid or sulfonic acid group. The amino group of those compounds may beunsubstituted but is preferably substituted, for example byunsubstituted or substituted C₁–C₄alkyl. Suitable substituents in thelatter case are especially hydroxy and carboxy. Suitable radicals ofaromatic amines are, for example, as follows:

alkyl being as defined hereinbefore, especially methyl.

Suitable coupling components are, for example, the usual couplingcomponents customarily used for azo dyes and known from the pertinentliterature, e.g. coupling components from the benzene series,naphthalene series, open-chain methylene-active compounds (e.g.acylacetarylamides) and the heterocyclic series.

They are, for example, acylacetarylamides, phenols, naphthols,pyridones, quinolones, pyrazoles, indoles, diphenylamines, anilines,aminopyridines, pyrimidones, naphthylamines, aminothiazoles, thiophenesor hydroxypyridines.

Acetoacetanilides, phenols, anilines, diphenylamines, naphthylamines,indoles, quinolines, pyridones, pyrazoles and aminopyridines areespecially suitable.

Such coupling components may carry further substituents, for exampleamino, alkylamino, dialkylamino, halogen, alkyl, alkoxy, aryl,especially phenyl or naphthyl, or aryloxy, but especially a groupimparting water solubility, e.g. hydroxy, carboxy, sulfo or aquaternised ammonium radical of formula (6) defined hereinbefore.

The coupling components preferably carry one or two such groupsimparting water solubility. Examples of suitable coupling components areas follows:

The amines of formulae A-NH₂ and B—NHR and the coupling components areknown or can be synthesised in a manner known per se.

The compounds of formulae (1), (2), (4) and (5) are also known or can besynthesised in a manner known per se.

The compounds of formula (3) wherein B is the radical of an aliphaticamine are likewise known or can be synthesised in a manner known per se.

The compounds of formula

wherein

-   A is the radical of an unsubstituted or substituted, water-soluble    aromatic or heterocyclic amine,-   B′ is the radical of an unsubstituted or substituted, water-soluble    aliphatic or aromatic amine and-   R is an unsubstituted or substituted alkyl group, are novel.

The definitions and preferred meanings mentioned under formulae (1) to(5) apply to A and R, and the definitions and preferred meaningsmentioned under formulae (1) to (5) apply to B′, insofar as they referto aromatic amines. The compounds of formula (7) can likewise beprepared in a manner known per se; for example, an amine of formulaA-NH₂ is, in customary manner, diazotised and coupled to an amine offormula B′—NHR, there coming into consideration as amines B—NH₂ onlythose compounds that couple at the nitrogen atom rather than at a carbonatom of the aromatic ring. Such compounds are, preferably, anilinederivatives substituted in the 4-position.

The first stage of the colouring method according to the inventioncomprises applying to the material being coloured, in any desired ordersuccessively, or simultaneously, a capped diazonium compound and awater-soluble coupling component under conditions such that, initially,coupling does not take place. That is accomplished, for example, byimmersing the material in a solution comprising the capped diazoniumcompound or the coupling component and then, optionally after rinsingand intermediate drying, immersing the material in a solution of thesecond component. Preferably, however, the capped diazonium compound andthe coupling component are contained together in one solution. It isalso possible for the solutions in question to be applied to thematerial by means of spraying or similar means, although it must beensured that there is adequate penetration unless it is desired tocolour only the upper layers. During that first stage the diazoniumcompound and the coupling component should not yet react with oneanother, which is achieved preferably by maintaining a pH of from 8 to12, especially from 9 to 11.

In the second stage, the diazonium compound and the coupling componentare then caused to react, preferably by lowering the pH to a value offrom 5 to 2, especially from 3 to 4. Lowering the pH is achieved inconventional manner by adding an acid, such as tartaric acid or citricacid, a citric acid gel, a suitable buffer solution or by means of anacid dye.

The ratio of the amount of alkaline colouring composition applied in thefirst stage to that of acid colouring composition applied in the secondstage is preferably about from 1:3 to 3:1, especially about 1:1.

The contact time is preferably about from five to thirty minutes in eachcase, especially from 10 to 20 minutes in each case.

The coloured material is then finished in customary manner, for exampleby rinsing with water and then drying.

The method according to the invention is suitable for all-over colouringof the hair, that is to say when colouring the hair on a first occasion,and also for re-colouring subsequently.

A preferred embodiment of the method according to the invention relatesto the colouring of porous material by bringing the material beingcoloured into contact with a capped diazonium compound and awater-soluble coupling component, in any desired order successively, orsimultaneously,

-   -   a) under alkaline conditions and optionally in the presence of a        further dye, preferably an oxidation dye, or a cationic, anionic        or uncharged direct dye, especially a cationic dye selected from        the group of the cationic dyes as described in WO 95/01772 and        WO 01/66646 and then subjecting the material being coloured to        treatment with acid, or    -   b) under alkaline conditions, and then subjecting the material        being coloured to treatment with acid, optionally in the        presence of a further dye, preferably an oxidation dye, or a        cationic, anionic or uncharged direct dye, especially a cationic        dye selected from the group of the cationic dyes as described in        WO 95/01772 and WO 01/66646, or    -   c) under alkaline conditions in the presence of an oxidising        agent, and optionally in the presence of a further dye,        preferably an oxidation dye, or a cationic, anionic or uncharged        direct dye, especially a cationic dye selected from the group of        the cationic dyes as described in WO 95/01772 and WO 01/66646        and then subjecting the material being coloured to treatment        with acid.

In the methods according to the invention, whether or not colouring isto be carried out in the presence of a further dye will depend upon thecolour shade to be obtained.

In the context of the present invention, the expression “alkalineconditions” denotes a pH in the range from 8 to 10, preferably 9–10,especially 9.5–10.

The alkaline conditions are customarily achieved by adding bases, forexample sodium carbonate, ammonia or sodium hydroxide, to the hair or tothe dye precursors, the capped diazonium compound and/or thewater-soluble coupling component, or to colouring compositionscomprising the dye precursors.

In the context of the present invention, oxidising agents are understoodto be any oxidising agent customarily used for oxidative hair colouring,for example dilute hydrogen peroxide solutions, hydrogen peroxideemulsions or hydrogen peroxide gels, alkaline earth metal peroxides,urea peroxides, melamine peroxides, especially dilute hydrogen peroxidesolutions.

The oxidising agents are used in appropriate stoichiometric amounts thatcorrespond to the total molar amounts of oxidation dye precursors.

The method according to the invention is used for colouring porousmaterial, for example wood, glass fibres, aluminium, cotton, paper,natural or synthetic polyamides, e.g. leather, wool, nylon or perlon,but especially keratin-containing fibres and more especially forcolouring hair. The hair may be the hair of wigs or, especially, theliving hair of animals and, more especially, humans.

The invention relates also to colouring compositions for carrying outthe method according to the invention, which compositions comprise

-   a) a compound of formula (1), (2), (3), (4) or (5) indicated    hereinbefore,-   b) a medium for adjusting the pH,-   c) water and, optionally,-   d) further additives.

Preferred compositions comprise

-   a) a compound of formula (1), (2), (3), (4) or (5) indicated    hereinbefore,-   b) a medium for adjusting the pH,-   c) water,-   d) a coupling component and, optionally,-   e) further additives.

Especially preferred compositions comprise

-   f) a compound of formula (1), (2), (3), (4) or (5) indicated    hereinbefore,-   g) a medium for adjusting the pH,-   h) water,-   i) a coupling component,-   j) a further dye, preferably an oxidation dye, or a cationic,    anionic or uncharged direct dye, especially a cationic dye selected    from the group of the cationic dyes as described in WO 95/01772 and    WO 01/66646, and, optionally,-   k) further additives.

Special preference is given to colouring compositions for the colouringof hair. Further additives that are suitable for such compositionsinclude additives that are customary in hair-colouring, for examplefurther dyes, surfactants, solvents, perfumes, polymeric adjuvants,thickeners and light stabilisers.

The diversity of shades and the colour fastness of the dye mixtures usedin accordance with the invention can be increased by combination withother dyes used in the field of hair-colouring compositions. They can becombined very readily both with oxidation dyes and with direct dyes, itbeing possible for the latter to be of anionic or cationic nature oruncharged.

In all colouring compositions, it is also possible for a plurality ofdifferent colourants to be used together; likewise, it is possible for aplurality of different oxidation dye precursors from the group of thedeveloper and coupler compounds to be used together, for examplearomatic compounds having a primary or secondary amino group,nitrogen-containing heterocycles, aromatic hydroxy compounds or aminoacids, as described, for example, in German Patent Application 197 17224.5.

The dye mixtures according to the invention produce colour shades in therange from yellow to blue, and the fastness properties are outstanding.Attention is drawn to the excellent fastness to light and fastness towashing properties and to their property that enables hair that hasalready been coloured a dark colour still to be distinctly altered inshade.

In a further embodiment, for the purpose of further modification ofcolour shades the colouring compositions according to the invention alsocomprise, in addition to the dye mixtures according to the invention,customary direct dyes, for example from the group of the nitroanilines,nitrophenylenediamines, nitroaminophenols, anthraquinones, indophenols,phenazines, phenothiazines and methines.

Also very suitable for combination with the dye mixtures according tothe invention are cationised nitroaniline and anthraquinone dyes, forexample those described in the following patent specifications: U.S.Pat. No. 5,298,029, U.S. Pat. No. 5,360,930, U.S. Pat. No. 5,169,403,U.S. Pat. No. 5,256,823, U.S. Pat. No. 5,135,543, EP-A-818 193, U.S.Pat. No. 5,486,629 and EP-A-758 547.

Also, cationic direct dyes such as cationic azo dyes, for exampleaccording to GB-A-2 319 776, as well as the oxazine dyes described inDE-A-299 12 327 and mixtures thereof with the other direct dyesmentioned therein, are likewise suitable for combination.

Cationic direct dyes, for example according to WO 95/01772, WO 95/15144,EP 714 954 and EP 318 294, are also suitable for combination.

In addition, the colouring compositions according to the invention mayalso comprise naturally occurring dyes, for example henna red, hennaneutral, henna black, camomile blossom, sandalwood, black tea, Rhamnusfrangula bark, sage, campeche wood, madder root, catechu, sedre andalkanet root. Such colouring methods are described, for example, inEP-A-404 868.

In respect of further customary dye components, reference is madeexpressly to the series “Dermatology”, edited by Ch. Culnan, H. Maibach,Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, TheScience of Hair Care, chapter 7, pages 248–250 (direct dyes), andchapter 8, pages 264–267 (oxidation dyes), and to “Europäisches Inventarder Kosmetikrohstoffe”, 1996, published by The European Commission,obtainable in diskette form from the Bundesverband der deutschenIndustrie- und Handelsunternehmen für Arzneimittel, Reformwaren undKörperpflegemittel e. V., Mannheim.

It is not necessary for the oxidation dye precursors, where present, orfor the dyes each to be single compounds, but rather the colouringcompositions according to the invention may additionally comprise,depending on the preparation procedures for the individual dyes, lesseramounts of further components, provided such components do not have anadverse effect on the colouring result or do not need to be excluded forother reasons, for example toxicological reasons.

The dye mixtures according to the invention may also readily be used incombination with other dyes and/or adjuvants used in the colouring ofhair, for example with

-   -   oxidising agents to achieve lightened colorations, as described        in EP-A-810 851,    -   oxidising agents in the form of permanent-wave fixing solution,        as described in DE-A-197 13 698 or WO 99/40895,    -   oxidation dyeing compositions, as described in EP-A-850 636,        EP-A-850 637, EP-A-850 638 and EP-A-852 135,    -   oxidation dyes in the presence of oxidoreductase enzyme, as        described in WO 99/17730 and WO 99/36034,    -   autooxidisable oxidation dyes, as described in WO 99/20234, or    -   nitrobenzene derivatives, as described in WO 99/20235.

The colouring compositions according to the invention produce intensecolorations even at physiologically tolerable temperatures of less than45° C. They are accordingly suitable especially for colouring humanhair. For use on human hair, the colouring compositions can usually beincorporated into an aqueous cosmetic carrier. Suitable aqueous cosmeticcarriers include, for example, creams, emulsions, gels and alsosurfactant-containing foaming solutions, e.g. shampoos or otherpreparations, that are suitable for use on keratin-containing fibres.Such forms of use are described in detail in Research Disclosure 42448(August 1999). If necessary, it is also possible to incorporate thecolouring compositions into anhydrous carriers, as described, forexample, in U.S. Pat. No. 3,369,970. The colouring compositionsaccording to the invention are also outstandingly suitable for thecolouring method described in DE-A-3 829 870 using a colouring comb orcolouring brush.

The colouring compositions according to the invention may furthermorecomprise any active ingredient, additive or adjuvant known for suchpreparations. The colouring compositions in many cases comprise at leastone surfactant, there being suitable in principle anionic and alsozwitterionic, ampholytic and non-ionic surfactants. In many cases,however, it has proved advantageous to select the surfactants fromanionic and non-ionic surfactants.

Anionic surfactants suitable for use in preparations according to theinvention include any anionic surface-active substance that is suitablefor use on the human body. Such a substance is characterised by ananionic group that imparts water solubility, for example a carboxylate,sulfate, sulfonate or phosphate group, and a lipophilic alkyl grouphaving approximately from 10 to 22 carbon atoms. In addition, glycol orpolyglycol ether groups, ester, ether and amide groups and also hydroxygroups may be present in the molecule. Examples of suitable anionicsurfactants, each in the form of sodium, potassium or ammonium salts ormono-, di- or tri-alkanolammonium salts having 2 or 3 carbon atoms inthe alkanol group, are:

-   -   linear fatty acids having from 10 to 22 carbon atoms (soaps),    -   ether carboxylic acids of formula R—O—(CH₂—CH₂—O)_(x)—CH₂—COOH,        in which R is a linear alkyl group having from 10 to 22 carbon        atoms and x=0 or from 1 to 16,    -   acyl sarcosides having from 10 to 18 carbon atoms in the acyl        group,    -   acyl taurides having from 10 to 18 carbon atoms in the acyl        group,    -   acyl isothionates having from 10 to 18 carbon atoms in the acyl        group,    -   sulfosuccinic acid mono- and di-alkyl esters having from 8 to 18        carbon atoms in the alkyl group and sulfosuccinic acid        monoalkylpolyoxyethyl esters having from 8 to 18 carbon atoms in        the alkyl group and from 1 to 6 oxyethyl groups,    -   linear alkanesulfonates having from 12 to 18 carbon atoms,    -   linear α-olefin sulfonates having from 12 to 18 carbon atoms,    -   α-sulfo fatty acid methyl esters of fatty acids having from 12        to 18 carbon atoms,    -   alkyl sulfates and alkyl polyglycol ether sulfates of formula        R′—O(CH₂—CH₂—O)_(x′)—SO₃H, in which R′ is a preferably linear        alkyl group having from 10 to 18 carbon atoms and x′=0 or from 1        to 12,    -   mixtures of surface-active hydroxysulfonates according to DE-A-3        725 030,    -   sulfated hydroxyalkylpolyethylene and/or        hydroxyalkylenepropylene glycol ethers according to DE-A-3 723        354,    -   sulfonates of unsaturated fatty acids having from 12 to 24        carbon atoms and from 1 to 6 double bonds according to DE-A-3        926 344,    -   esters of tartaric acid and citric acid with alcohols that are        addition products of approximately from 2 to 15 molecules of        ethylene oxide and/or propylene oxide with fatty alcohols having        from 8 to 22 carbon atoms.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ethersulfates and ether carboxylic acids having from 10 to 18 carbon atoms inthe alkyl group and up to 12 glycol ether groups in the molecule, andalso especially salts of saturated and especially unsaturatedC₈–C₂₂carboxylic acids, such as oleic acid, stearic acid, isostearicacid and palmitic acid.

The term “zwitterionic surfactants” denotes surface-active compoundsthat carry at least one quaternary ammonium group and at least one—COO⁽⁻⁾ or —SO₃ ⁽⁻⁾ group in the molecule. Zwitterionic surfactants thatare especially suitable are the so-called betaines, such as theN-alkyl-N,N-dimethylammonium glycinates, for examplecocoalkyldimethylammonium glycinate,N-acylaminopropyl-N,N-dimethylammonium glycinates, for examplecocoacylaminopropyidimethylammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines each having from 8 to18 carbon atoms in the alkyl or acyl group and alsococoacylaminoethylhydroxyethylcarboxymethyl glycinate. A preferredzwitterionic surfactant is the fatty acid amide derivative known by theCTFA name cocamidopropyl betaine.

Ampholytic surfactants are to be understood as meaning surface-activecompounds that, in addition to a C₈–C₁₈-alkyl or -acyl group, contain atleast one free amino group and at least one —COOH or —SO₃H group in themolecule and are capable of forming internal salts. Examples of suitableampholytic surfactants include N-alkylglycines, N-alkylpropionic acids,N-alkylaminobutyric acids, N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines,N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoaceticacids, each having approximately from 8 to 18 carbon atoms in the alkylgroup. Ampholytic surfactants to which special preference is given areN-cocoalkylaminopropionate, cocoacylaminoethylaminopropionate andC₁₂–C₁₈acylsarcosine.

Non-ionic surfactants contain as the hydrophilic group, for example, apolyol group, a polyalkylene glycol ether group or a combination ofpolyol and polyglycol ether groups.

Such compounds are, for example:

-   -   addition products of from 2 to 30 mol of ethylene oxide and/or        from 0 to 5 mol of propylene oxide with linear fatty alcohols        having from 8 to 22 carbon atoms, with fatty acids having from        12 to 22 carbon atoms and with alkylphenols having from 8 to 15        carbon atoms in the alkyl group,    -   C₁₂–C₂₂ fatty acid mono- and di-esters of addition products of        from 1 to 30 mol of ethylene oxide with glycerol,    -   C₈–C22alkyl-mono- and -oligo-glycosides and ethoxylated        analogues thereof,    -   addition products of from 5 to 60 mol of ethylene oxide with        castor oil and hydrogenated castor oil,    -   addition products of ethylene oxide with sorbitan fatty acid        esters,    -   addition products of ethylene oxide with fatty acid        alkanolamides.

The alkyl-group-containing compounds used as surfactants may be singlesubstances, but the use as starting materials of natural raw materialsof vegetable or animal origin is generally preferred in the preparationof such substances, with the result that the substance mixtures obtainedhave different alkyl chain lengths according to the particular startingmaterial used.

The surfactants that are addition products of ethylene and/or propyleneoxide with fatty alcohols or derivatives of such addition products mayeither be products having a “normal” homologue distribution or productshaving a restricted homologue distribution. “Normal” homologuedistribution is to be understood as meaning mixtures of homologuesobtained in the reaction of fatty alcohol and alkylene oxide usingalkali metals, alkali metal hydroxides or alkali metal alcoholates ascatalysts. Restricted homologue distributions, on the other hand, areobtained when, for example, hydrotalcites, alkali metal salts of ethercarboxylic acids, alkali metal oxides, hydroxides or alcoholates areused as catalysts. The use of products having restricted homologuedistribution may be preferred.

Examples of further active ingredients, adjuvants and additives are:

-   -   non-ionic polymers, for example vinylpyrrolidone/vinyl acrylate        copolymers, polyvinyl pyrrolidone and vinylpyrrolidone/vinyl        acetate copolymers and polysiloxanes,    -   zwitterionic and amphoteric polymers, for example        acrylamidopropyl-trimethylammonium chloride/acrylate copolymers        and octylacrylamide/methyl methacrylate/tert-butylaminoethyl        methacrylate/2-hydroxypropyl methacrylate copolymers,    -   anionic polymers, for example polyacrylic acids, crosslinked        polyacrylic acids, vinyl acetate/crotonic acid copolymers,        vinylpyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl        maleate/isobornyl acrylate copolymers, methyl vinyl ether/maleic        anhydride copolymers and acrylic acid/ethyl        acrylate/N-tert-butyl acrylamide terpolymers,    -   thickeners, such as agar, guar gum, alginates, xanthan gum, gum        arabic, karaya gum, locust bean flour, linseed gums, dextrans,        cellulose derivatives, e.g. methyl cellulose, hydroxyalkyl        cellulose and carboxymethyl cellulose, starch fractions and        derivatives, such as amylose, amylopectin and dextrins, clays,        e.g. bentonite or fully synthetic hydrocolloids such as, for        example, polyvinyl alcohol,    -   structuring agents, such as glucose and maleic acid,    -   hair-conditioning compounds, such as phospholipids, for example        soya lecithin, egg lecithin and cephalins, silicone oils, and        also conditioning compounds, for example such as those described        in DE-A-197 29 080, EP-A-834 303 or EP-A-312 343,    -   protein hydrolysates, especially elastin, collagen, keratin,        milk protein, soya protein and wheat protein hydrolysates,        condensation products thereof with fatty acids and also        quaternised protein hydrolysates,    -   perfume oils, dimethyl isosorbitol and cyclodextrins,    -   solubilisers, such as ethanol, isopropanol, ethylene glycol,        propylene glycol, glycerol and diethylene glycol,    -   anti-dandruff active ingredients, such as piroctone, olamines        and Zinc Omadine,    -   further substances for adjusting the pH,    -   active ingredients such as panthenol, pantothenic acid,        allantoin, pyrrolidonecarboxylic acids and salts thereof, plant        extracts and vitamins,    -   cholesterol,    -   light stabilisers and UV absorbers, as described, for example,        in EP-A-819 422,    -   consistency regulators, such as sugar esters, polyol esters or        polyol alkyl ethers,    -   fats and waxes, such as spermaceti, beeswax, montan wax,        paraffins, fatty alcohols and fatty acid esters,    -   fatty acid alkanolamides,    -   polyethylene glycols and polypropylene glycols having a        molecular weight of from 150 to 50 000, for example such as        those described in EP-A-801 942,    -   complexing agents, such as EDTA, NTA and phosphonic acids,    -   swelling and penetration substances, such as polyols and polyol        ethers, as listed extensively, for example, in EP-A-962 219, for        example glycerol, propylene glycol, propylene glycol monoethyl        ether, butyl glycol, benzyl alcohol, carbonates, hydrogen        carbonates, guanidines, ureas and also primary, secondary and        tertiary phosphates, imidazoles, tannins, pyrrole,    -   opacifiers, such as latex,    -   pearlising agents, such as ethylene glycol mono- and        di-stearate,    -   propellants, such as propane-butane mixtures, N₂O, dimethyl        ether, CO₂ and air, and also    -   antioxidants, for example isoascorbic acid, ascorbic acid,        sodium sulfite, thioglycolic acid and thiolactic acid.

The constituents of the aqueous carrier are used in the preparation ofthe colouring compositions according to the invention in the amountscustomary for that purpose; for example emulsifiers are used inconcentrations of from 0.5 to 30% by weight and thickeners inconcentrations of from 0.1 to 25% by weight of the total colouringcomposition.

To colour keratin-containing fibres, especially to colour human hair,the colouring compositions are usually applied to the hair in an amountof from 50 to 100 g in the form of the aqueous cosmetic carrier, left onthe hair for approximately 30 minutes and then rinsed off or washed offwith a commercially available hair shampoo.

The colouring compositions used in accordance with the invention and theoptionally used oxidation dye precursors may be applied to thekeratin-containing fibres either simultaneously or successively, theorder in which they are applied being unimportant.

The colouring compositions used in accordance with the invention and theoptionally used oxidation dye precursors may be stored either separatelyor together, either in a liquid to paste-like preparation (aqueous ornon-aqueous) or in the form of a dry powder. When the components arestored together in a liquid preparation, the preparation should besubstantially anhydrous in order to reduce reaction of the components.When they are stored separately, the reactive components are intimatelymixed with one another only immediately before use. In the case of drystorage, before use a defined amount of hot (from 50 to 80° C.) water isusually added and a homogeneous mixture prepared.

The following Examples serve to illustrate the invention withoutlimiting the invention thereto. Unless specified otherwise, parts andpercentages relate to weight. The amounts of dye specified are relativeto the material being coloured.

EXAMPLE 1

A) Preparation of Triazenes

43.4 g of 4-chloro-2-amino-1-methylbenzene are mixed with 81 g of 32%hydrochloric acid and cooled to 0° C. Then, over the course of one hour,75 ml of 4N aqueous sodium nitrite solution are added dropwise, withstirring, the temperature being maintained at from 0 to 5° C. Theresulting solution is then added dropwise, over the course of 15minutes, to an aqueous solution of 30 g of sarcosine and 90 g of sodiumcarbonate in 250 ml of water at a temperature of 0–5° C. The resultingbrown suspension is filtered, the residue is recrystallised from ethanoland dried in air. 66.2 g of3-methyl-1-(5-chloro-2-methylphenyl)-3-(carboxylmethyl)triazene areobtained in the form of brownish-yellow powder. (Yield: 91%). Thecompound has the following formula and its ¹H-NMR spectrum exhibits thechemical shifts indicated.

EXAMPLES 2 TO 4

Using a procedure analogous to that described in Example 1, thefollowing compounds are prepared:

Example 2 3 4

Colouring Method A:

A strand of bleached human hair is immersed, for 30 minutes at roomtemperature, in an aqueous solution containing 0.2M triazene and 0.2Mcoupling component, which has been adjusted to pH 10.0 using sodiumcarbonate, ammonia or NaOH. The strand is removed, excess solution iswiped off and the strand is immersed for 5 minutes in a pH 3 buffersolution containing 4% sodium citrate and 2% citric acid. The strand isthen thoroughly rinsed using water and, where appropriate, a shampoosolution and is dried. Hair coloured in the shades mentioned isobtained, with outstanding fastness properties, especially fastness towashing properties.

Colouring Method B:

A strand of bleached human hair is immersed, for 30 minutes at roomtemperature, in an aqueous solution that contains 0.2M triazene, 0.2Mcoupling component and 0.2M of hydrogen peroxide (6%) and that has beenadjusted to a pH in the range pH 9.8–10 using sodium carbonate, ammoniaor NaOH. After contact for 5–30 minutes, there is applied to the strand,without its being rinsed, an amount, corresponding to the weight oftriazene and coupling component originally used, of a mixture comprising12.5% strength aqueous citric acid gel, which contains 0.1% by weight ofa cationic dye selected from the group of the cationic dyes as disclosedin WO 95/01772 and in WO 01/66646. The strand is then combed throughthoroughly, a pH of about 7 being obtained. After contact for 15minutes, the treated strand is treated again with the above mixturecomprising 12.5% strength citric acid gel and 0.1% by weight of acationic dye selected from the group of the cationic dyes as disclosedin WO 95/01772 and in WO 01/66646 at pH 4 for 5 minutes, rinsedthoroughly with water and then dried. Hair is obtained with outstandingfastness properties, especially fastness to washing and fastness toshampooing properties.

Colouring Method C:

A strand of bleached human hair is immersed, for 30 minutes at roomtemperature, in an aqueous solution that contains 0.2M triazene, 0.2Mcoupling component and 0.2 mol of hydrogen peroxide (6%) and that hasbeen adjusted to a pH in the range pH 9.8–10 using sodium carbonate,ammonia or NaOH. After contact for 5–30 minutes, there is applied to thehair, without its being rinsed, an amount, corresponding to the weightof triazene and coupling component originally used, of a 12.5% strengthaqueous citric acid gel containing 0.1% by weight of a cationic dyeselected from the group of the cationic dyes as disclosed in WO 95/01772and in WO 01/66646 and 4% sodium citrate; the hair is combed throughthoroughly, a pH of about 3 being obtained. Then, after a contact timeof 5–30 minutes, the hair is rinsed thoroughly with water and dried.Hair is obtained with outstanding fastness properties, especially goodfastening to washing properties.

Colouring Method D:

A strand of bleached human hair is immersed, for 30 minutes at roomtemperature, in an aqueous solution containing 0.2M triazene, 0.2Mcoupling component, 0.2 mol of hydrogen peroxide (6%) and from 0.1 to 1%by weight, based on the weight of the triazene and coupling component,of a cationic dye selected from the group of the cationic dyes asdescribed in WO 95/01772 and in WO 01/66646. The strand is then adjustedto a pH in the range pH 9.8–10 using sodium carbonate, ammonia or NaOH.After contact for 5–30 minutes, there is applied to the hair, withoutits being rinsed, an amount, corresponding to the weight of triazene andcoupling component originally used, of a 12.5% strength aqueous citricacid gel and 4% sodium citrate and the hair is combed throughthoroughly, a pH of about 3 being obtained. Then, after a contact timeof 5–30 minutes, the hair is rinsed thoroughly with water and dried.Hair is obtained with outstanding fastness properties, especially goodfastness to washing properties.

Triazene Coupler Hair colour Example 5:

carmine-red Example 6:

cherry-red Example 7:

reddishorange Example 8:

magenta Example 9:

violet Example 10:

burgundy-red Example 11:

ruby-red Example 12:

yellow-ochre Example 13:

chestnut-brown Example 14:

copper-red Example 15:

brilliant orange Example 16:

greenish brown Example 17:

lemon-yellow Example 18:

reddish orange Example 19:

golden-yellow Example 20:

copper-red Example 21:

copper-red Example 22:

rust-red Example 23:

wine-red Example 24:

mid-brown Example 25:

pink Example 26:

violet Example 27:

blue-black Example 28:

copper-red Example 29:

copper-coloured Example 30:

purple Example 31:

blue Example 32:

blue Example 33:

violet Example 34:

red Example 35:

vivid yellow Example 36:

scarlet Example 37:

copper-red Example 38:

vivid red Example 39:

brownishviolet Example 40:

carmine-red Example 41:

dark-brown Example 42:

brownishorange Example 43:

vivid red Example 44:

vivid yellow Example 45:

yellowish orange Example 46:

reddishorange Example 47:

lemon-yellow Example 48:

straw-yellow Example 49:

brownishorange Example 50:

dullorange Example 51:

reddishorange Example 52:

vividred Example 53:

neutralred Example 54:

cherry-red Example 55:

purplishblack Example 56:

vividyellow Example 57:

dullyellow Example 58:

greenishbrown Example 59:

yellowishorange Example 60:

ruby-red Example 61:

purered Example 62:

reddishpurple Example 63:

violet Example 64:

reddishbrown Example 65:

red Example 66:

red Example 67:

red

EXAMPLE 68

A strand of bleached human hair is treated with a mixture of equal partsby weight—5 g in each case—of 6% hydrogen peroxide solution and ofcomposition A.

Composition A: cetyl stearyl alcohol 11.00 oleth-5 5.0 oleic acid 2.5stearic acid monoethanolamide 2.5 coconut fatty acid monoethanolamide2.5 sodium lauryl sulfate 1.7 1,2-propanediol 1.0 ammonium chloride 0.5EDTA, tetrasodium salt 0.2 perfume 0.4 wheat protein hydrolysate 0.2silica 0.1 2,5-diaminotoluene sulfate 0.7 4-amino-2-hydroxytoluene 0.52,5,6-triamino-4-hydroxypyrimidine sulfate 0.2 sodium sulfite 1.0ascorbic acid 0.5 triazene of Example 30 9.32 coupler of Example 3011.52 composition A: pH 9.8 water ad 100

After contact for 15 minutes at room temperature, about 22° C., 10 g ofa mixture of a 12.5% strength aqueous citric acid gel containing 0.1% byweight of a violet dye of the following formula

which is prepared analogously to WO 01/66646, Example 4, is applied tothe strand. The strand is then combed through, whereupon a pH of about 7is achieved. After contact for a further 15 minutes, the strand is againtreated with 10 g of the above mixture of citric acid gel and violetdye, whereupon a pH of about 4 is achieved. The mixture is allowed toact for 5 minutes at pH 4 and the strand is then washed with water andshampoo and then again with water. The strand is then dried.

A strong, intense, striking violet coloration having good fastness towashing and fastness to rubbing properties is obtained.

EXAMPLE 69

A strand of medium-blond human hair is coloured with a mixture of equalparts by weight—5 g in each case—of 6% hydrogen peroxide solution and ofcomposition A according to Example 68.

The mixture is allowed to act on the strand for 30 minutes at roomtemperature, about 22° C. 10 g of a mixture of a 2% strength aqueouscitric acid gel containing 0.1% by weight of a violet dye according tothe above formula in Example 68, and 4% sodium citrate, are then appliedto the strand. The strand is then combed through, whereupon a pH ofabout 3 is achieved. After contact for 5 minutes, the strand isthoroughly rinsed and then dried.

A strong, intense, striking violet coloration having good fastness towashing and fastness to rubbing properties is obtained.

EXAMPLE 70

A strand of bleached human hair is coloured with a mixture of equalparts by weight—5 g in each case—of 6% hydrogen peroxide solution and ofcomposition B.

Composition B: cetyl stearyl alcohol 11.00 oleth-5 5.0 oleic acid 2.5stearic acid monoethanolamide 2.5 coconut fatty acid monoethanolamide2.5 sodium lauryl sulfate 1.7 1,2-propanediol 1.0 ammonium chloride 0.5EDTA, tetrasodium salt 0.2 perfume 0.4 wheat protein hydrolysate 0.2silica 0.1 triazene of Example 30 9.32 coupler of Example 30 11.52composition B: pH 9.8 water ad 100

The mixture is allowed to act on the strand for 30 minutes at about 22°C. 10 g of a mixture of a 2% strength aqueous citric acid gel containing0.1% by weight of a violet dye according to the above formula in Example68, and 4% sodium citrate, are then applied to the strand. The strand isthen combed through, whereupon a pH of about 3 is achieved. Aftercontact for 5 minutes, the strand is thoroughly rinsed and then dried.

A strong, intense, striking violet coloration having good fastness towashing and fastness to rubbing properties is obtained.

EXAMPLE 71

A strand of blond undamaged human hair is coloured with a mixture ofequal parts by weight—5 g in each case—of 6% hydrogen peroxide solutionand of composition C.

Composition C: cetyl stearyl alcohol 11.00 oleth-5 5.0 oleic acid 2.5stearic acid monoethanolamide 2.5 coconut fatty acid monoethanolamide2.5 sodium lauryl sulfate 1.7 1,2-propanediol 1.0 ammonium chloride 0.5EDTA, tetrasodium salt 0.2 perfume 0.4 wheat protein hydrolysate 0.2silica 0.1 violet dye of Example 68 0.2 triazene of Example 30 9.32coupler of Example 30 11.52 composition C: pH 9.8 water ad 100

The mixture is allowed to act on the strand for 30 minutes at about 22°C. 10 g of a mixture of a 2% strength aqueous citric acid gel containing0.1% by weight of a violet dye according to the above formula in Example68, and 4% sodium citrate, are then applied to the strand; the latter isthen combed through, whereupon a pH of about 3 is achieved. Aftercontact for 5 minutes, the strand is thoroughly rinsed and then dried.

A strong, intense, striking violet coloration having good fastness towashing and fastness to rubbing properties is obtained.

EXAMPLE 72

A strand of blond undamaged human hair is coloured with 10 g ofcomposition D.

Composition D: cetyl stearyl alcohol 11.00 oleth-5 5.0 oleic acid 2.5stearic acid monoethanolamide 2.5 coconut fatty acid monoethanolamide2.5 sodium lauryl sulfate 1.7 1,2-propanediol 1.0 ammonium chloride 0.5EDTA, tetrasodium salt 0.2 perfume 0.4 wheat protein hydrolysate 0.2silica 0.1 violet dye of Example 68 0.2 triazene of Example 30 4.66coupler of Example 30 5.76 composition D: pH 10 water ad 100

The mixture is allowed to act on the strand for 30 minutes at about 22°C. 10 g of a mixture of a 2% strength aqueous citric acid gel containing4% sodium citrate are then applied to the strand; the latter is thencombed through, whereupon a pH of about 3 is achieved. After contact for5 minutes, the strand is thoroughly rinsed and then dried. A strong,intense, striking violet coloration having good fastness to washing andfastness to rubbing properties is obtained.

EXAMPLE 73

A strand of blond undamaged human hair is coloured with 10 g ofcomposition E.

Composition E cetyl stearyl alcohol 11.00 oleth-5 5.0 oleic acid 2.5stearic acid monoethanolamide 2.5 coconut fatty acid monoethanolamide2.5 sodium lauryl sulfate 1.7 1,2-propanediol 1.0 ammonium chloride 0.5EDTA, tetrasodium salt 0.2 perfume 0.4 wheat protein hydrolysate 0.2silica 0.1 triazene of Example 36 4.66 coupler of Example 36 5.76composition E: pH 10 water ad 100

The mixture is allowed to act on the strand for 30 minutes at about 22°C. Then 10 g of a mixture of a 2% strength aqueous citric acid gelcontaining 0.1% by weight of a red dye of the following formula

which can be prepared, for example, as described in WO 01/11708,according to Preparation Example 6, compound of formula 106,

-   and 4% sodium citrate, are applied to the strand and then combed    through, whereupon a pH of about 3 is achieved. After contact for 5    minutes, the strand is thoroughly rinsed and then dried.

A strong, intense, striking scarlet coloration having good fastness towashing and fastness to rubbing properties is obtained.

EXAMPLE 74

A strand of blond undamaged human hair is coloured with 10 g ofcomposition F.

Composition F cetyl stearyl alcohol 11.00 oleth-5 5.0 oleic acid 2.5stearic acid monoethanolamide 2.5 coconut fatty acid monoethanolamide2.5 sodium lauryl sulfate 1.7 1,2-propanediol 1.0 ammonium chloride 0.5EDTA, tetrasodium salt 0.2 perfume 0.4 wheat protein hydrolysate 0.2silica 0.1 triazene of Example 36 5.3 coupler of Example 36 5.2composition F: pH 10 water ad 100

After contact for 30 minutes, without being washed out, a dye mixtureknown from U.S. Pat. No. 6,248,314 and having the following composition:

Black Color No. 401 0.1 Purple Color 401 0.05 Orange Color No. 205 0.1benzyl alcohol 2.0 ethylene carbonate 10 propylene carbonate 15 ethanol10 lactic acid 3.5 sodium carbonate solution of pH 2.9 hydroxyethylcellulose 1.5 water ad 100is applied to the hair. The hair is then combed through thoroughly,whereupon its pH becomes about 3. Then, after a contact period of 15minutes, the hair is rinsed thoroughly with water and dried.

A strong, intense, striking red coloration having good fastness towashing and fastness to rubbing properties is obtained.

EXAMPLE 75

A strand of blond undamaged human hair is coloured with 10 g of acomposition comprising compositions A and B.

Compositions A B C cetyl stearyl alcohol 11.00 11.00 11.00 oleth-5 5.05.0 5.0 oleic acid 2.5 2.5 2.5 stearic acid monoethanolamide 2.5 2.5 2.5coconut fatty acid monoethanolamide 2.5 2.5 2.5 sodium lauryl sulfate1.7 1.7 1.7 1,2-propanediol 1.0 1.0 1.0 ammonium chloride 0.5 0.5 0.5EDTA, tetrasodium salt 0.2 0.2 0.2 perfume 0.4 0.4 0.4 wheat proteinhydrolysate 0.2 0.2 0.2 silica 0.1 0.1 0.1 2,5-diaminotoluene sulfate0.7 4-amino-2-hydroxytoluene 0.5 2,5,6-triamino-4-hydroxypyrimidine 0.2sulfate sodium sulfite 1.0 ascorbic acid 0.5 triazene of Example 30 9.32coupler of Example 30 11.52 composition: pH 10 10 10 water ad 100 ad 100ad 100

The colouring mixture is allowed to act on the hair for 30 minutes atabout 22° C. 10 g of a 2% strength aqueous citric acid gel are thenapplied to the strand. After contact for 5 minutes, the strand is rinsedthoroughly, shampooed and then dried.

A strong, intense, striking coloration having good fastness to washingand fastness to rubbing properties is obtained.

EXAMPLE 76

A strand of blond undamaged human hair is coloured with a mixture of 15g of 6% hydrogen peroxide solution and a composition consisting of 5 geach of compositions A, B and C according to Example 75.

The colouring mixture is allowed to act on the hair for 30 minutes atabout 22° C. 10 g of a 2% strength aqueous citric acid gel are thenapplied to the strand. After contact for 5 minutes, the strand is rinsedthoroughly, shampooed and then dried.

A strong, intense, striking coloration having good fastness to washingand fastness to rubbing properties is obtained.

1. A method of colouring hair, which comprises applying to the hairbeing coloured, in any order successively, or simultaneously, a cappeddiazonium compound and a water-soluble coupling component a) underalkaline conditions and optionally in the presence of a further dye, andthen subjecting the hair being coloured to treatment with acid, or b)under alkaline conditions, and then subjecting the hair being colouredto treatment with acid, optionally in the presence of a further dye,wherein there is used as the capped diazonium compound an antidiazoateof formula

a diazosulfonate of formula

a diazine of formula

or a cyclic triazene of formula

wherein A is the organic residue of an unsubstituted or substitutedaromatic or heterocyclic amine and B is the radical of an unsubstitutedor substituted, water-soluble aliphatic or aromatic amine, wherein atleast one of the above groups must contain a radical imparting watersolubility.
 2. A method according to claim 1, which comprises bringingthe hair being coloured into contact with a capped diazonium compoundand a water-soluble coupling component, in any desired ordersuccessively, or simultaneously, c) under alkaline conditions in thepresence of an oxidising agent and optionally in the presence of afurther dye, and then subjecting the hair being coloured to treatmentwith acid, or d) under alkaline conditions, and then subjecting the hairbeing coloured to treatment with acid, optionally in the presence of afurther dye.
 3. A method according to claim 1, wherein the radicalimparting water solubility is SO₃H, COOH, OH or a quaternised ammoniumradical of formula

wherein R_(1,) R₂ and R₃ are each independently of the othersunsubstituted or substituted alkyl and An is an anion.
 4. A methodaccording to claim 1, wherein A is the organic residue of anunsubstituted or substituted aminobenzene, 1- or 2-aminonaphthalene,2-aminothiophene, 2-amino-1,3-thiazole, 5-amino-1,2-thiazole,2-amino-1,3-benzothiazole, 1-amino-2,3-benzothiazole, 2-aminoimidazole,2-amino-1,3,4-thiadiazole, 2-amino-1,3,5-thiadiazole,2-amino-1,3,4-triazole, 3-, 7- or 8-aminopyrazole, 2-aminobenzimidazole,2-aminobenzopyrazole, 2- or 4-aminopyridine, 2-, 3-, 4-, 7- or8-aminoquinoline, 2-aminopyrimidine and 3-aminoisoxazole,5-aminoquinoline, 4-aminodiphenylamine, 2-aminodiphenyl ether or4-aminoazobenzene.
 5. A method according to claim 4, wherein the radicalA is unsubstituted or is mono- or poly-substituted by C_(1–C) ₄alkyl,C₁–C₄alkoxy, C₁–C₄alkylthio, halogen, nitro, trifluoromethyl, CN, SCN,C₁–C₄alkylsulfonyl, phenylsulfonyl, benzylsulfonyl,di-C₁–C₄alkylaminosulfonyl, C₁–C₄alkylcarbonylamino, C₁–C₄alkoxysulfonylor by di-(hydroxy-C₁–C₄alkyl)-aminosulfonyl.
 6. A method according toclaim 1, wherein B is the radical of an aliphatic amine carrying acarboxylic acid or sulfonic acid group and optionally carrying furthersubstituents.
 7. A method according to claim 6, wherein B is the radicalof an aniline or aminonaphthalene compound carrying a carboxylic acid orsulfonic acid group and optionally carrying further substituents.
 8. Amethod according to claim 1, wherein there is used as the couplingcomponent an unsubstituted or substituted acylacetarylamide, phenol,naphthol, pyridine, quinolone, pyrazole, indole, diphenylamine, aniline,aminopyridine, pyrimidone, naphthylamine, aminothiazole, thiophene orhydroxypyridine.
 9. A method according to claim 8, wherein a couplingcomponent mono- or poly-substituted by amino, alkylamino, dialkylamino,halogen, alkyl, alkoxy, phenyl, naphthyl or by aryloxy is used.
 10. Amethod according to claim 8, wherein a coupling component mono- orpoly-substituted by a group imparting water solubility, is used.